Methyl 5-O-acetyl-3,4-O-cyclohexylidenequinate | 168784-04-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: Methyl 5-O-acetyl-3,4-O-cyclohexylidenequinate
• 英文别名: methyl (3aR,5S,7R,7aR)-7-acetyloxy-5-hydroxyspiro[4,6,7,7a-tetrahydro-3aH-1,3-benzodioxole-2,1'-cyclohexane]-5-carboxylate
• CAS: 168784-04-1
• 化学式: C₁₆H₂₄O₇
• 分子量: 328.362
• InChiKey: FZVZGDQPSQSPQU-GUIRCDHDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  23
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  91.3
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  Methyl 5-O-acetyl-3,4-O-cyclohexylidenequinate 在 吡啶 、 三氯氧磷 作用下， 反应 3.0h， 生成 methyl (3aR,7R,7aS)-7-acetyloxyspiro[3a,6,7,7a-tetrahydro-1,3-benzodioxole-2,1'-cyclohexane]-5-carboxylate
  参考文献：
  名称：

  Construction of the Bicyclic Core Structure of the Enediyne Antibiotic Esperamicin-A1 in Either Enantiomeric Form from (-)-Quinic Acid

  摘要：

  Employed as a common chiral starting material, (-)-quinic acid (7) was converted in a concise manner to both enantiomers of the beta,gamma-unsaturated ketone 12. On the one hand, (+)-12 was obtained by stereospecific borohydride reduction of the conjugated ketone intermediate 9, transketalization, and oxidation of the derived homoallylic alcohol using the Dess-Martin periodinane reagent. Alternatively, dehydration of the tertiary alcohol 13 and oxidation of the free hydroxyl group in 14 furnished (-)-12 in good overall yield. Reaction of (+)-12 with dichlorocerium TMS acetylide was followed by Pd(0)-assisted construction of the acyclic enediyne 21. Cyclization of this intermediate on treatment with KHMDS proved efficient, providing the esperamicin intermediate (-)-22 in 60% isolated yield. In an identical fashion -)-12 was converted to the enantiomeric bicyclic enediyne (+)-22. Subsequent liberation of the diol system, and selective oxidation of the allylic alcohol in 25 gave ketone 26. Reaction of this intermediate with Ph(2)S=NH monohydrate gave aziridine 27 which was readily converted to its carbamate derivative 28 in preparation for aziridine ring opening.

  DOI：

  10.1021/jo00114a025
• 作为产物：
  描述：

  methyl 3,4-O-cyclohexylidenequinate 、 乙酸酐 在 吡啶 作用下， 以 二氯甲烷 为溶剂， 以88%的产率得到Methyl 5-O-acetyl-3,4-O-cyclohexylidenequinate
  参考文献：
  名称：

  Studies toward the construction of the allyltrisulfide Component in esperamicin-A1 from 5-ketoshikimic acid derivatives: Part 1

  摘要：

  The conversion of keto ester 1, obtained in either enantiomeric form from (-)-quinic acid to its corresponding enol silyl ether 4 was examined as the first step to construct the allyl trisulfide unit found in esperamicin A,. Under different conditions a very facile dimerization of either 4 or enolate 10 to give compound 14 was observed. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(98)02399-5